Apparatus for gas analysis



Jan. 29, 1946. w, M, ZAIKOWSKY 2,393,674

APPARATUS FOR GAS ANALYSIS Filed June 26, 1959 3 Sheets-Sheet l Q 5 E k b PUR/FY/NG TEA //v 3 VACUUM INVENTOR. ZA/KO waxy BY M WTORNEYS.

Jan. 29, 1946. w. M. ZAIKOWSKY 2,393,674

APPARATUS FOR GAS ANALYSIS Filed June 26, 1939 3 Sheets-Sheet 2 INVENTOR. WLAD/M/R M Z A mews/(r BY QM.

A TTORNEYS.

1946. w. M. ZAIKOWSKY APPARATUS FOR GAS ANALYSIS Filed June 26, 1939 3 Sheefcs-Sheet 3 INVENTOR. MAD/Mm MZA/KO wsKY ATTORNEYS.

Patented Jan. 29, 1946 UNITED STATES PATENT OFFICE 2.303.014 g APPARATUS FOR GAS ANALYSIS Wladimir M. Zaikowsky, Pasadena, Calif., assignor, by Inesne assignments, to Consolidated Enginee Pasadena,

ring Corporation.

poratlon of California Application June 26, 1939, Serial No. 281,128

4 Claims. (Cl. 23-254) My invention relates to gas analysis and more particularly to a means and method of analyzing a gas in order to determine the presence of certain hydrocarbons therein.

Among the objects of my invention are: to provide a means and method of gas analysis distinguishing hydrocarbons indicative of oil deposits, from hydrocarbons known to have other origins; to provide a means and method of gas analysis which will indicate the presence of ethane or the higher parafilns, even when methane and ethylene are also present; to provide a means and method of gas analysis automatically recording volumetric changes due to combustion; to provide a means and method of distinguishing between methane and ethylene as one group, and the higher parafiins as another group in a gas sample; to provide a means and method of detecting other hydrocarbons in the presence of methane and ethylene; to provide a mean and method of distinguishing, in a soil gas sample hydrocarbons indicative of oil deposits, from hydrocarbons which are bacteriological and vegetable by-products; and, to provide a simple direct reading gas analysis device ideally adapted for use when total hydrocarbon concentration is small.

My invention possesses numerous other objects and features of advantage, some of which, to-

gether with the foregoing, will be set forth in the following description of specific apparatus embodying and utilizing my novel method. It is therefore to be understood that my method is applicable to other apparatus, and that I do not limit myself, in any way, to the apparatus, of the present application, as I may adopt various other apparatus embodiments, utilizing the meth-- od, within the scope of the appended claims.

In the drawings, J s

Figure l is a diagrammatic representation of one preferred system for obtaining purified soil Figure 2 is a diagram forming a continuation of the diagram of Figure 1, showing the means by which I obtain volumetric changes in accordance with the gas present.

Figure 31s a. diagrammatic representation of an automatic recording device applicable to the system shown in Figure 2.

Referring directly to Figure 1 a soil or gas sample III is collected in the field, preferably below the water table, and placed in a wide mouthed Jar II. A large number of such samples may be collected in the field over an area Cali! acorto be prospected, from systematically located points of which records are kept. Each sample is sealed in its ownjar, labeled, and brought into ample, activated charcoal or silica gel. The sample Ill when connected to a gas line It is first frozen by means of liquid air it contained in vacuum bottle 20. Container Il may then be evacuated to remove air therefrom. Gas chamber ll, isolated from the remainder of the system by main stop cock 2|, may also be evacuated. Liquid air trap 20 may then be removed from container II and applied to chamber ll. Thereafter various amounts of heat may be applied to sample III to cause gas to emanate therefrom which gas is collected in chamber ll. At least a partial fractionation may be made in this manner, as desired, by application of various temperatures to the original sample.

Stop cock l5 may then be utilized to isolate the gas sample in chamber H from the original soil, and stop cock 2| be opened to admit gas from container ll together with an oxygen bearing as if desired through line Hi into a purifying train 22 wherein, by methods well known in the art, H2 and CO and other undesired impurities are removed. After the gas has passed through purifying train 22, it is passed through an inverted trap 24 surrounded by solid CO2, whose evaporation rate is controlled by a vacuum line 26 in such a manner that the temperature of trap 24 is maintained at approximately -90 to --100 C. This temperature will remove water, vapor from'the gas sample without condensing any substantial amount of such hydrocarbon gas present as Idesire to indicate. The purified gas thus obtained is collected in purified as container 21 which has previously been evacuated by vacuum line 29, container 21 being provided with a liquid air envelope 30. Thus various purified fractions from the original soil sample may be collected in container 21 if desired at any pressure desired. v

The purified fraction in container 21 may then be isolated from the purifying train by stop cock SI and allowed to pass into combustion chamber 32 through line and stopcock 4|.

Combustion chamber 32 is a tube roughly describing an oval, and is provided on one leg of the oval with a cooling chamber 54. On the other leg of the chamber is a coil 35 mounted in an expanded portion 38. This coil is preferably made of platinum wire wound in tapered helical form and without exterior connections. The helix is preferably heated from outside of the combustion chamber by an infra red lamp ll or'by induction if preferred. The base of helix 55 overlies and surrounds a jet 39. Combustion chamber 32 is also provided at one end thereof between cooling chamber 84 and helix 35 with a portion 44 sealed by an unstable diaphragm 45,

otherwise known as a click diaphragm, in that changes in pressure on one side thereof will cause distortion into a new position with an audible click, this distortion reversing when the pressure is reversed a predetermined amount, with the same sound. The opposite end of the combustion chamber is provided with a capillary tube 45 filled with a mercury column to a defined level from a mercury container 41 connected with capillary tube 46 by flexible tube 49, as shown in Figure 3. The remaining details of the mercury column will be described later.

Returning to Figure 2, diaphragm 45 is positioned within a chamber 50 connected to a check chamber 5| which is an exact duplicate of combustion chamber 32 except for the fact that there is no capillary tube attached thereto and contains helix 35 and provided with cooling chamber 34'.

Referring to Figure 3 for additional details of the mercury column controlling device, mercury container 41 is mounted on wheel rotated by motor 15 at a relatively slow and uniform speed. The radial distance of mercury container 41 from the center of rotation, is such as to periodioally raise and lower mercury column il in capillary tube 46 a sumcient amount to cause diaphragm 45 to click into both upper and lower positions acting through the gas in the combustion chamber. In as much as I prefer to continuously record the upper and lower positions of the mercury column at each diaphragm choking time I position, adjacent diaphragm 45, a pickup microphone 62 energizing an amplifier 54 whose output energizes a mercury arc tube 55 at each click. This tube passes light through a slit 65 on to film 61, this film being continuously and uniformly progressed by driving sprocket 59. Mercury column 6|, however, is positioned between slit 66 and film 61 and move parallel thereto and obscures a portion of the slit. In as much as light 65 will only be energized when the click occurs, ends 3-13 of recorded lines II on film 61 will show the positions of the mercury column at the times the clicks occur before combustion. All of the apparatus shown in Figures 2 and. 3 should preferably be enclosed in a temperature controlled container I" (see Fig. 2) to eliminate effects of temperature distribution and to maintain the water of combustion in vapor phase during measurement.

It is clear that theme syphon circulation in each of the chambers 32 and 5| will start as soon as platinum coils 35 and 35 are heated even if coolers 54 and 34 are not used, in which case the maintenance of both chambers at the same temperature will be facilitated by any suitable means.

Assume now that the gas sample to be analwed has been admitted to combustion chamber 3! aaoac'u through stop cock 4| and that check chamber I has also been filled with gas, such as for example, air at a pressure balancing the unstable diaphragm 45 in a position enabling pressure changes caused by movement of the mercury column to click the diaphragm at the upper and lower limits of its movement. The infra red lamp 51 of the combustion chamber and lamp 31 of the check chamber, are energized to heat platinum spirals I5 and 35'. Circulation of gas around the combustion chamber and around the check chamber will then start due to the differential temperatures in the chambers. This circulating action is due to the combined action of the diiferential temperatures and gravity and is the type known as thermo-syphon circulation. As spiral 35 increases in temperature, combustion of the hydrocarbon within combustion chamber 32 will take place, utilizing the catalytic action of the platinum wire, and oxygen which has aocompanied the gas. No combustion takes place in the check chamber because of the lack of combustible material therein.

During the time of circulation and combustion in the combustion chamber, the clicks of diaphragm 45 may be irregular and this portion of the record is omitted in Figure 3. As soon as combustion is completed however, the clicks will stabilize. As there has not been any change in volume of the gas due to combustion within the check chamber then any change in volume in the combustion chamber will cause a displacement in the choking positions of the mercury column. This shift in clicking relationship will be registered on the film as shown by lines II and 12. Thus an increase in volume due'to combustion is indicated by the distance between lines A and B in Figure 3, and this dilference indicates that ethane, propane, etc, were present. The important fact is that the presence of methane or ethylene in no way obscures the results obtained.

The following formulas are examples of various oxidation reactions which may occur:

For methane:

CH4+201=C02+2H20 3 vols.=3 vols. For ethylene:

C2H4+302=2CO2+2H2O 4 vols==4 vols. For ethane:

CzHs+3.50z=2CO2+3H2O 4.5 vols-=5 vols. For propane:

C3Hs+502=3CO2+4H2O 6 vols=7 vols.

Any change in volume that occurs is a measure of the change in molal quantity or molal volume of the gas.

As has been stated the gas admitted to each chamber is dried suflloiently so as to prevent the condensation of water which will be formed in the combustion of hydrocarbons. The observance of this point is essential and the temperature surrounding both chambers should be so correlated with the amount of water vapor; formed in combustion so that no condensation occurs. If a small quantity of water vapor is produced in the combustion chamber 32, the temperature Of the chamber wall, even if at room temperature, will be suillciently high to prevent condensation of the water of combustion. In case suflicient water is produced tending to condense water vapor in the chamber 3!,the temperature of a temperature control chamber lurroundingtheapparatusmayberaisedtolucba ascaovs degree that the excess water vapor otherwise tending to condense will be maintained in vapor phase.

After a recording has been made, giving the click positions with relation to the mercury column, both before and after combustion, the analyzed sample may be withdrawn through line 42, and a new sample may be admitted to combustion chamber 32 and the cycle repeated.

Thus I am able to take a sample containing or suspected of including ethane in addition to methane and ethylene, and determine whether or not ethane or other hydrocarbons indicative of oil deposits are present, by determining whether or not an increase of volume occurs after combustion. If such an increase occurs then ethane and such other hydrocarbons are present, if no increase in volume occurs then none or the hydrocarbons such as ethane are present in the original sample.

As previously described, in order to assure myself that the reaction and the results obtained will be reliable, I remove, if present, hydrogen and carbon monoxide during purification, as these gases give a reduction in volume, which might counteract any increase in volume created by the presence of ethane, for example. v

Thus, I have been able to determine the presence or absence oi ethane, propane, etc., in mixtures containing ethylene or methane. It should be pointed out here that this distinction can not be made in such mixtures by routine analysis, without an extremely long and complicated process. which is many times impossible to accbmplish because of the small hydrocarbon concentration available in the original soil sample.

Also it will be obvious to those skilled in the art that my described means and method is valuable in determining the presence of ethane. etc., even when no ethylene or methane is present.

I claim:

is sufilciently and suddenly deformed. means for introducing and maintaining a gas to be analyzed in the first of the chambers, a first heating means within that chamber for producing combustion of the gas to be analyzed, valved conduits communicating with the interior of the secend or the chambers, a second heating means enclosing both chambersior maintaining the two chambers at substantially identical temperatures, a tube leading into the first of the chambers, means for reciprocating a confining liquid within that tube to vary the efi'ective volume 0! the first chamber and the pressure difierential between the two sides of the diaphragm to produce a sudden change in the position of the diaphragm, means associated with the tube capable of periodically recording the positions of the confining liquid in the tube during the reciprocation of this liquid, and means responsive to the sounds of the sudden changes of the diaphragm position and associated with the lastnamed means for actuating the same to record small changes 01 vol e resulting from the combustion of the gas undergoing analysis.

3. In apparatus for micro-analysis of gas, the combustion which comprises a first chamber having a valved conduit connected thereto for admission of gas and means for efiecting combustion or the gas in the chamber, a second closed comparison chamber, a .conduit between the chambersclosed by a click-type diaphragm, a

- continuously operable pressure generating means 1. Apparatus for analysis or soil gas for hydrocarbons indicative oi petroleum deposits, comprising puriiying train means for removing hydrogen and carbon monoxide from th gas to be analyzed, combustion chamber, a valved conduit connecting said means to said combustion chamber for transfer 01' gas from said means to said combustion chamber, first heating means mounted within said combustion chamber for oxidizing said gas in said combustion chamber, measuring means associated with said combustion chamber adapted to indicate changes in the moiai volume or said gas, and second heating means enclosing said combustion chamber for maintaining the water of combustion in vapor phase during such measurement.

2. Apparatus for micro-analysis of gas comprising two similar chambers whose interiors are separated by a pressure-sensitive click-type diaphragm capable of producing sound when it constructed to impart reciprocating pressure impulses to said first chamber, a conduit containing a liquid connected to said first chamber and said pressure generating means as to impart the reciprocating impulses to said fiuid, means for measuring and indicating movement of liquid in said conduit, and sound sensitive means responsive to the snapping of said diaphragm arranged to effect the operation of said indicating means.

4. In apparatus for micro-analysis of gas, the combination which comprises a chamber having a valved conduit connected thereto i'or admission of gas and means for eii'ecting combustion of the gas in the chamber, a click-type diaphragm forming part oi the wall or the chamher and movable from one position to another with change of pressure within the chamber, a continuously operable pressure generating means constructed to impart reciprocating pressure impulses to the chamber, a conduit containing a liquid so connected to the chamber and to the pressure-generating means as to impart the reciprocating impulses to the fluid,

means for measuring and indicating movement of liquid in said conduit, and sound sensitive means responsive to the snapping of the diaphragm arranged to effect the operation of said indicating means.

WLADIMIR M. ZAIKOWBKY. 

